Manufacture of alkyl phenols



Patented July 7, 1936 i i I UNITED STATES PATENT OFFICE -9 9 MANUFACTURE or Anni. PHENOLS marmr Ipatieii, Chicago, 111.; assignor to Universal Oil Products Company, Chicago, 111., a corporation of Delaware No Drawing. Application February 11, 1933,

Sena] No. 658,373

This invention relates to the manufacture of Table ICnii1m1ed hydrocarbon derivatives and refers more partlc- Y ularly to the manufacture of compounds of a o ring character containing both alkyl and, hy-. Name Formula MP. 0' B?- O I droxyl groups.

More specifically the invention has reference mydm Puma QR to a process for manufacturing alkyl" deriva-v 01 "-011 133 doc. 29a. tives of the class oi. compounds known generally 10 as phenols which comprises either mono or poly 10 nuclear ring compounds containing hydroxyl 0H P J 1 OxyhydroquinonM... -on 140.5

The phenols constitute an important class of chemical compounds which occur -in varying 15 amounts in the products obtained-when distilling n various carbonaceous materials such as coal, on shale lignite, peat, wood, etc. Many of these Pmommdno] Y m individual compounds and the commercial mi:;- 1

tures obtained from primary distillation proda 1 QH ucts have value as germicides and insecticides v and as base products for the manufacture of 1 The invention further com rises the manufacmore complicated Substances such for ture oi derivatives of poly nu clear phenolswhich ample, various resinous condensation products a v are characterized by such compounds as alpha pmduced by reacting Phemls and aldehydes' naphthol with. a melting point 01 94 c. and a .The-followinetable Elves [the boiling point of 2'19" 0. and beta naphthol with mono nuclear P 01 "W a melting point of 122 c. and a boiling point or hydric character. 285.5 C.

m Tabla! 'In one specific embodiment the present invvention'comprises the production of alkyl derivatives of phenolic'compounds by treatment or Name Formula LIL/PFC. B. P. 0. the same with oleflns in the presence oi phosphoric acid. r

' I have discovered that the alkylation of phenols on a may be accomplished with greatly improved efllciency by using phosphoric acid instead of .such previously used condensing agents as sulphuric a I acid and heavy metal chlorides including alumi- Dlhydflfl P on num and zinc chlorides. when using such re- 40 A agents the reactions of alkylation are attended PyrocatechDL- 104 240-6 by various types of undesirable side reactions a which decrease the yield of desired products.

Mono-hydric phenols:

Phenol "I-.- 43 '183 For example, with sulphuric acid of sumcient 1 5 on Y concentrationtoproduce material yields of alkyl- 45 a ated derivatives of phenols there is always an ,Rwmml a .undesirable amount or sulphonation and tar on formation. with aluminum chloride and similar compounds there is also a considerable loss I v on v i on account of the formation of addition com- K dm inone... g in 2st pounds of an intermediate character which grad-' I ually resiniiyto produce heavy residues of no value. I I H 7 In contrast to the dimculties experienced .pre-

viously the use otphosphoric acid (and other suitable acids of phosphorus) according to the process of the present invention minimizes'the side reactions and produces high yields of compounds of-the desired character, to wit; phenols with ring hydrogen atoms substituted by alkyl residues. While the commoner acids of phosphorus such as the well known ortho phosphoric acid and ortho phosphorous acid are generally preferable on account of their ready availability and moderate cost, it is also comprised within the scope of the invention to employ any of the acids of phosphorus alone or in admixture insofar as beneficial and economical results are obtainable thereby. These alternative reagents are not proposed as exact equivalents since to anyone sufficiently conversant with the chemical art it is obvious that, each will exert its own particular effect in any given case. In the table below a tabulation of the names, formulas and commoner Ortho phosphoria. H:P P O RH O In producing alkyl derivatives of phenols ac-.

cording to the process of the present invention the exact mode of procedure will vary with the nature of the reacting constituents. A very simpleprocedure in the case of phenols which are fiuid in moderately elevated temperatures and olefins which are gaseous or readily vaporized, consists in passing theolefin vapor into a suspension of phosphoric acid in the phenol, intimate contacting of the reacting compounds with acid catalyst being .assured by either vigorous mechanical agitation or the forcible injection of the vapors in the form of fine bubbles. Where the phenol is substantially non-volatile at temperatures slightly above its melting point itwill usual- .ly be unnecessary to employ pressure higher than ordinary atmospheric, though superatmospheric pressures may be employed if economy is gained thereby or the rate of reaction is increased. This type of operation is essentially a batch procedure, the introduction of the olefin vapor being continued until the desired degree of alkylation is when phenols are treated with olefins in the presthe production of gasoline or of fuel gas.

was as follows:

ence of acids of phosphorus is illustrated by the following equations:

. 1 canon oim Big t .H. 5

Phenol Propylene 0H Iso-propylphenol OH CiHi cm. cm. mp0. elm-on CH Ethylene CH:

Creso) Methyl-ethyl phenol Reactions of the above character may be made to occur in predominating amounts, frequently 95% of the phenol being thus converted. Limited amounts of diand tri-substituted products may also be produced.

The process may be employed to effect the reaction between chemical individuals comprising phenols on the one hand and olefins on the other or it may be employed to produce mixtures of alkylated products by using either phenolic mixtures or olefinic mixtures or both. For example,

' a mixture of alkylated derivatives may be produced by reacting the tar-acids separated from various crude tars by caustic alkali (and later acidification) with olefin-containing gas mixtures such for example as those encountered in oil cracking processes either aimed primarily at.

Mixtures thus produced may find application as germicidal, insecticidal or disinfecting material or may in some cases be employed as inhibitors or anti-oxidants for preventing the formation of gummy and resinous polymers from the olefins contained in such materials as cracked gasoline or commercial fuel gases. It is a matter of frequent observation though not always a general rule that the presence of aliql substituting groups in phenols corresponds to increased inhibiting value. For example,phenol itself has a relatively low value for preventing the deterioration of cracked gasoline upon storage whereas a mixture of cresols commonly known as tri-cresol'. has greatly increased value in this respect. The substitution of alkyl residues of higher molecular weight than the methyl residue, for example, the butyl residue, has been observed to still further increase the value as inhibitors of the base phenolic substances. The following examples illustrate results obtainable in alkylating various phenols at atmospheric pressure, though it is understood that these are merely illustrative and can be supplemented by a number of further instances.

effected, at which time the stream ofv vapor is' stopped and the acid catalyst allowed to settle,

A mixture of 70 parts by weight of phenol and 30 parts by weight of 89% phosphoric acid 1 was vigorously agitated and subjected to treatment with propylene gas at temperatures of from 120 to 130 C. and atmospheric pressure until approximately 34 parts by weight of propylene were absorbed, this corresponding to somewhat more than the theoretical weight of propylene necessary for forming the mono iso propyl substitution product. There was substantially no polymer or tar formation and the products of the reaction were completely soluble in 15% aqueous caustic soda. The distillation test of the product 2,040,900 3 Percent phenols to the action of an oleflnic compound Fraction -205 0 6 in the presence of an acid of phosphorus. Fraction 205-220 C 43 2. A process for the treatment of pyrocatechol Fraction 220-230 C Fraction 230-242 C Higher boiling fraction.

Example 2 Inhibitor Induction period m-crmol min. 225-235 0. propyiated iractiom- 85 min. 235-27)? 0. propylatod traction..- 310 min.

The foregoing specification and numerical data adduced in support of the operability and utility of the invention are sufiiclent for their respective purposes but are not to be considered in'a narrow sense as imposng undue limitations on the generally broad scope of the invention.

I claim as my invention:

1. A process for the treatment of di-hydric phenols to produce albl derivatives thereof which comprises, subjecting the said di-hydric to produce alkyl derivatives thereof which comprises, subjecting the said pyrocatechoi to the ac- 3 tion of an olefinlc compoimd in the presence of an acid of phosphorus.

3. 'A process for the treatment-oi a mixture of phenols to produce alkyl derivatives thereof which comprises, subjecting the said mixture to the action of a gaseous oleflnic compound in the presence oi phosphoric acid.

4. A process for the treatment of a mixture of phenols to produce alkyl derivatives thereof which comprises, subjecting the said mixture to the action of a cracked hydrocarbon gas in the presence of phosphoric acid.

5. A process for the treatment of poly-hydric phenols to produce alkyl derivatives thereof which comprises subjecting the p yydric phe- 2o n01 to the action of an oleflnic compound in the presence of an acid of phosphorus.

6. A process for the treatment of poly-hydric phenols to produce alkyl derivatives thereof which comprises subjecting the poiy-hydric 25 phenol to the action of an olefinic gas in the presence of phosphoric acid.

'1. A process for the treatment of resorcinol to produce an alkyl derivative thereof which comprises subjecting the same to the action of an oleflnic compound in the presence of an acid of phosphorus.

8. A process for th treatment of hydroquinone to produce an allwl derivative thereof which comprises subjecting the same to the action of 35 an oleflnic compound in the presence of'an acid of phosphorus.

VLADIMIR IPA'I'IEFF. 

